CN110501194B - Preparation method and application of methane combustible ice of sand filling pipe in laboratory - Google Patents
Preparation method and application of methane combustible ice of sand filling pipe in laboratory Download PDFInfo
- Publication number
- CN110501194B CN110501194B CN201910741440.5A CN201910741440A CN110501194B CN 110501194 B CN110501194 B CN 110501194B CN 201910741440 A CN201910741440 A CN 201910741440A CN 110501194 B CN110501194 B CN 110501194B
- Authority
- CN
- China
- Prior art keywords
- methane
- sand
- combustible ice
- pipe
- filling pipe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 493
- 239000004576 sand Substances 0.000 title claims abstract description 144
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 230000008014 freezing Effects 0.000 claims abstract description 28
- 238000007710 freezing Methods 0.000 claims abstract description 28
- 239000004744 fabric Substances 0.000 claims abstract description 27
- 229920000742 Cotton Polymers 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000002347 injection Methods 0.000 claims abstract description 17
- 239000007924 injection Substances 0.000 claims abstract description 17
- 238000006073 displacement reaction Methods 0.000 claims description 42
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000011435 rock Substances 0.000 claims description 11
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000005259 measurement Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 7
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 6
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011160 research Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 229940117955 isoamyl acetate Drugs 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229940094941 isoamyl butyrate Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 9
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004781 supercooling Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 58
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000011549 displacement method Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/22—Fuels; Explosives
- G01N33/225—Gaseous fuels, e.g. natural gas
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Tires In General (AREA)
Abstract
The invention discloses a preparation method of combustible methane ice for a sand-filled pipe in a laboratory, which comprises the steps of dissolving methane in a methane dissolving agent to obtain a saturated methane solution; and then uniformly mixing the methane solution and sand grains, adding the mixture into a sand filling pipe, compacting, wrapping cotton or cloth which is wetted by water outside the sand filling pipe, and placing the sand filling pipe in a refrigerator or a freezer for freezing for 2-3 days to obtain the methane combustible ice of the sand filling pipe. The invention provides a simple and rapid method and experimental device for selecting the optimal combustible ice rapid supercooling nano liquefying agent, the optimal injection mode and the optimal injection speed, and provides technical and theoretical bases for selecting the optimal method for exploiting combustible ice methane gas.
Description
Technical Field
The invention relates to the technical field of laboratory research of combustible ice, in particular to a preparation method and application of methane combustible ice of a sand filling pipe in a laboratory.
Background
At present, the conventional petroleum and natural gas resources stored in the world are greatly consumed and face exhaustion, and new energy needs to be developed urgently. Natural Gas Hydrate (Gas Hydrate for short) is ice-like crystalline substance which is distributed in deep sea sediments or permafrost in land areas and is formed by Natural Gas and water under high pressure and low temperature conditions, and the distribution range is very wide. The evaluation results of scientists show that the combustible ice distribution area is up to 4000 ten thousand square kilometers in the submarine region only, and the total area of the earth ocean is 1/4. Also, under standard conditions, a unit volume of natural gas hydrate decomposes to produce up to 164 unit volumes of methane gas. Therefore, the problem that oil resources are completely developed at the present stage can be effectively solved by developing combustible ice energy, and the most important thing for developing combustible ice is to develop laboratory research of combustible ice, so that reliable basis is provided for industrial exploitation of combustible ice.
However, the existing laboratory methods for producing combustible ice require extremely harsh high-pressure, low-temperature conditions. And although a stable combustible ice crystal sample can be synthesized by adopting in-situ neutron diffraction, the charging, discharging, sealing and metering of combustible ice methane gas are difficult problems.
Therefore, how to simplify the method for preparing combustible ice and how to charge, store and measure methane gas is a problem which needs to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of methane combustible ice for a sand-filled pipe in a laboratory, which can realize the generation of methane combustible ice in the sand-filled pipe, and the obtained methane combustible ice for the sand-filled pipe can be used for an experiment for displacing methane gas produced by combustible ice, and can measure and calculate the displacement efficiency. Firstly, increasing the dissolved amount of methane in water, and calculating the dissolving rate of methane gas in water by using the dissolved amount of methane gas; generating methane combustible ice in the sand filling pipe; then, 0.8-1.4% combustible ice is used for rapidly supercooling the nano liquefying agent to displace the sand filling pipe for generating the methane combustible ice, the gas quantity of the methane is measured by a drainage gas production method, and the displacement efficiency is calculated.
In order to achieve the purpose, the invention adopts the following technical scheme:
a methane dissolving agent MST comprises the following components in percentage by weight: 0-40% of diethylene glycol butyl ether, 0-10% of tert-butyl alcohol, 0-20% of polypropylene glycol, 0-15% of polyvinyl alcohol, 0-10% of sodium dodecyl sulfate, 0-23% of ethylene glycol ethyl ether acetate, 0-11% of ethyl acetoacetate, 0-40% of diethylene glycol butyl ether, 0-40% of diethylene glycol ethyl ether, 0-40% of isoamyl butyrate, 0-40% of isoamyl acetate, 0-40% of isooctyl acrylate and 0-40% of butyl butyrate, and the balance of water is added to make up 100%.
The invention also provides a method for generating the methane combustible ice of the sand-filled pipe, which comprises the following steps:
(1) weighing the raw materials by the methane dissolving agent, and uniformly mixing to obtain the methane dissolving agent;
(2) dissolving methane in a methane dissolving agent to obtain a saturated methane solution;
(3) uniformly mixing the methane solution and sand grains to thoroughly soak the sand grains, adding the mixture into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe in a refrigerator or a freezer for freezing to obtain methane combustible ice of the sand filling pipe; the water-soaked cotton or cloth ensures that the methane combustible ice of the sand filling pipe is always kept in a combustible ice frozen state during subsequent displacement.
Preferably, the temperature of the dissolving process in the step (2) is 15-25 ℃, and the pressure is 1.0 multiplied by 105Pa; the volume ratio of the methane to the methane dissolving agent is (0.1-20.0): 1.0.
preferably, the volume ratio of the methane solution to the sand grains in the step (3) is (1-2): (3-6); the thickness of the cotton or the cloth is 3cm-5cm, and the freezing temperature is set to be
The freezing time is 2-3 days.
Preferably, the sand grains comprise sand grains obtained by grinding combustible ice formation rock or sand grains prepared according to formation mineral components.
The invention also provides the sand-filled methane combustible ice which is prepared by the method as claimed in the claim.
The application of the sand-filled pipe methane combustible ice in laboratory research on combustible ice.
A method for applying the methane combustible ice of the sand-filled pipe specifically comprises the following steps:
(1) calculating the total volume Q1 of dissolved methane in the sand-packed pipe;
(2) displacing the methane combustible ice of the sand-filled pipe by using the injection liquid according to the rock sample seepage characteristics measured in a laboratory or a displacement experiment method carried out in the laboratory, collecting methane gas and measuring the volume of the methane gas to be Q2;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: the displacement efficiency is Q2/Q1 multiplied by 100%.
Preferably, the step (1) specifically comprises:
(11) measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; the formula B is that R ═ VMethane/VWater (W)；
(12) Calculating the total volume Q1 of dissolved methane in the sand-packed pipe
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1 ═ VWet×R。
According to the technical scheme, compared with the prior art, the preparation method and the application of the methane combustible ice for the sand-filled pipe in the laboratory have the following beneficial effects:
(1) the method provides a simple and feasible method for generating methane combustible ice for the sand-filled pipe in a laboratory, can manufacture the sand-filled pipe according to mineral components or real rock powder of a combustible ice rock stratum, generates the combustible ice sand-filled pipe in simulation of real formation pressure, real formation temperature and real formation rock, and provides technical and theoretical bases for selecting an optimal combustible ice rapid supercooling nano liquefying agent, an optimal injection mode, an optimal injection speed and an optimal method for exploiting combustible ice methane gas
(2) The sand-filled pipe methane combustible ice prepared by the method disclosed by the invention can be used for researching combustible ice in a laboratory and simulating the actual exploitation environment of the combustible ice, and has profound practical significance.
(3) The application method of the sand-packed pipe combustible ice disclosed by the invention can accurately calculate the displacement efficiency of exploiting the combustible ice by adopting the injection liquid to displace, so that the practicability of the injection liquid and the displacement exploitation method can be scientifically and accurately evaluated, the experiment cost can be reduced, and the experiment efficiency can be improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a methane dissolving agent MST, which comprises the following components in percentage by weight: 0-40% of diethylene glycol butyl ether, 0-10% of tert-butyl alcohol, 0-20% of polypropylene glycol, 0-15% of polyvinyl alcohol, 0-10% of sodium dodecyl sulfate, 0-23% of ethylene glycol ethyl ether acetate, 0-11% of ethyl acetoacetate, 0-40% of diethylene glycol butyl ether, 0-40% of diethylene glycol ethyl ether, 0-40% of isoamyl butyrate, 0-40% of isoamyl acetate, 0-40% of isooctyl acrylate and 0-40% of butyl butyrate, and the balance of water is added to make up 100%.
Example 1
The embodiment 1 of the invention provides a method for generating methane combustible ice of a sand-filled pipe, which specifically comprises the following steps:
(1) weighing the raw materials by the methane dissolving agent, and uniformly mixing to obtain the methane dissolving agent;
(2) dissolving methane in a methane dissolving agent to obtain a saturated methane solution; the temperature in the dissolving process is 15-25 ℃, and the pressure is 1.0 multiplied by 105Pa; the volume ratio of the methane to the methane dissolving agent is as follows;
(3) and uniformly mixing the methane solution and the sand grains to thoroughly soak the sand grains, adding the mixture into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe or the cloth in a refrigerator or a freezer for freezing to obtain the methane combustible ice of the sand filling pipe. The volume ratio of the methane solution to the sand grains is that the volume ratio of the methane solution to the sand grains is 1: 5; the thickness of the cotton or the cloth is 5cm, the freezing temperature is set to be-10 ℃, and the freezing time is 2 d.
In order to further optimize the technical scheme, the sand grains comprise sand grains obtained by grinding combustible ice stratum rocks or sand grains prepared according to stratum mineral components.
Example 2
The embodiment 2 of the invention discloses a method for applying the sand-filled pipe methane combustible ice, which specifically comprises the following steps:
(1) calculating the total volume Q1 of dissolved methane in the sand-packed pipe
(11) Measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; the formula B is that R ═ VMethane/VWater (W)；
(12) Calculating the total volume Q1 of dissolved methane in the sand-packed pipe
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1 ═ VWet×R。
(2) Displacing the methane combustible ice of the sand-filled pipe by using the injection liquid, wherein the displacement method is carried out according to a laboratory core holder displacement method, collecting methane gas and measuring the volume of the methane gas to be Q2;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: the displacement efficiency is Q2/Q1 multiplied by 100%.
Example 3:
the embodiment 3 of the invention discloses a method for generating methane combustible ice of a sand-filled pipe in a laboratory and a displacement gas production method.
A method for generating methane combustible ice of a sand-packed pipe specifically comprises the following steps:
(1) weighing the following raw materials in percentage by mass: mixing 10% of polypropylene glycol and 90% of water uniformly to obtain a methane dissolving agent;
(2) dissolving methane in the firstObtaining saturated methane solution in the alkane dissolving agent; the temperature and pressure during the dissolution process are 20 deg.C and 1.0 × 105Pa; methane solubility at 10% polypropylene glycol was 24.8%;
(3) and uniformly mixing the methane solution and the sand grains to thoroughly soak the sand grains, adding the mixture into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe or the cloth in a refrigerator or a freezer for freezing to obtain the methane combustible ice of the sand filling pipe. The volume ratio of the methane solution to the sand grains is that the volume ratio of the methane solution to the sand grains is 1: 5; the thickness of the cotton or the cloth is 5cm, the freezing temperature is set to be-10 ℃, and the freezing time is 2 d; the sand grains comprise the following components in percentage by mass: 95% quartz and 5% sodium bentonite.
A method for applying the methane combustible ice of the sand-filled pipe specifically comprises the following steps:
(2) calculating the total volume of dissolved methane in the sand-filled pipe;
(11) measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; the formula B is that R ═ VMethane/VWater (W)；
(12) The total volume Q1 of the dissolved methane in the sand-packed pipe is calculated to be 17.1ml
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1 ═ VWet×R。
(2) Displacing the methane combustible ice of the sand-filled pipe by using injection liquid according to a displacement method of a laboratory core holder, wherein the displacement condition is-10 ℃, a displacement agent is 2% diethylene glycol + 2% diethylene glycol dimethyl ether, and collecting methane gas and measuring the volume of the methane gas to be Q2-14.8 mL;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: the displacement efficiency is Q2/Q1 multiplied by 100 percent, 86.5 percent.
Example 4
The embodiment 4 of the invention discloses a method for generating methane combustible ice of a sand-filled pipe in a laboratory and a displacement gas production method.
A method for generating methane combustible ice of a sand-packed pipe specifically comprises the following steps:
(1) weighing the following raw materials in percentage by mass: mixing 10% of tert-butyl alcohol and 90% of water uniformly to obtain a methane dissolving agent;
(2) dissolving methane in a methane dissolving agent to obtain a saturated methane solution; the temperature and pressure during the dissolution process are 20 deg.C and 1.0 × 105Pa; the solubility of methane in 10% tert-butanol was 15.6%;
(3) and uniformly mixing the methane solution and the sand grains to thoroughly soak the sand grains, adding the mixture into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe or the cloth in a refrigerator or a freezer for freezing to obtain the methane combustible ice of the sand filling pipe. The volume ratio of the methane solution to the sand grains is that the volume ratio of the methane solution to the sand grains is 1: 5; the thickness of the cotton or the cloth is 5cm, the freezing temperature is set to be-10 ℃, and the freezing time is 2 d; the sand grains comprise the following components in percentage by mass: 95% quartz and 5% kaolinite.
A method for applying the methane combustible ice of the sand-filled pipe specifically comprises the following steps:
(3) calculating the total volume of dissolved methane in the sand-filled pipe;
(11) measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; the formula B is that R ═ VMethane/VWater (W)；
(12) The total volume Q1 of the dissolved methane in the sand-packed pipe is calculated to be 10.8ml
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1 ═ VWet×R。
(2) Displacing the sand-filled pipe methane combustible ice by using injection liquid according to a displacement method of a laboratory core holder, wherein the displacement condition is-10 ℃, a displacing agent is 6% HCl, and methane gas is collected and measured, and the volume of the methane gas is Q2-8.9 ml;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: the displacement efficiency is Q2/Q1 multiplied by 100 percent, 82.4 percent.
Example 5
The embodiment 5 of the invention discloses a method for generating methane combustible ice of a sand-filled pipe in a laboratory and a displacement gas production method.
A method for generating methane combustible ice of a sand-packed pipe specifically comprises the following steps:
(1) weighing the following raw materials in percentage by mass: 10% of polyvinyl alcohol and 90% of water are uniformly mixed to obtain a methane dissolving agent;
(2) dissolving methane in a methane dissolving agent to obtain a saturated methane solution; the temperature and pressure during the dissolution process are 20 deg.C and 1.0 × 105Pa; the solubility of methane in 10% polyvinyl alcohol is 22.1%;
(3) and uniformly mixing the methane solution and the sand grains to thoroughly soak the sand grains, adding the mixture into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe or the cloth in a refrigerator or a freezer for freezing to obtain the methane combustible ice of the sand filling pipe. The volume ratio of the methane solution to the sand grains is that the volume ratio of the methane solution to the sand grains is 1: 5; the thickness of the cotton or the cloth is 5cm, the freezing temperature is set to be-10 ℃, and the freezing time is 2 d; the sand grains comprise the following components in percentage by mass: 95% quartz and 5% illite.
A method for applying the methane combustible ice of the sand-filled pipe specifically comprises the following steps:
(4) calculating the total volume of dissolved methane in the sand-filled pipe;
(11) measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; said formula BIs R ═ VMethane/VWater (W)；
(12) The total volume Q1 of the dissolved methane in the sand-packed pipe is calculated to be 15.2ml
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1 ═ VWet×R。
(2) Displacing the sand-filled pipe methane combustible ice by using an injection liquid according to a laboratory core holder displacement method under the displacement condition of-10 ℃, using a displacement agent of 6% propionic acid, collecting methane gas and metering the volume of the methane gas to be Q2-12.3 ml;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: the displacement efficiency is Q2/Q1 multiplied by 100 percent, 80.9 percent.
Example 6
The embodiment 6 of the invention discloses a method for generating methane combustible ice of a sand-filled pipe in a laboratory and a displacement gas production method.
A method for generating methane combustible ice of a sand-packed pipe specifically comprises the following steps:
(1) weighing the following raw materials in percentage by mass: mixing 10% of sodium dodecyl sulfate and 90% of water uniformly to obtain a methane dissolving agent;
(2) dissolving methane in a methane dissolving agent to obtain a saturated methane solution; the temperature and pressure during the dissolution process are 20 deg.C and 1.0 × 105Pa; the solubility of methane in 10% sodium lauryl sulfate was 18.2%;
(3) and uniformly mixing the methane solution and the sand grains to thoroughly soak the sand grains, adding the mixture into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe or the cloth in a refrigerator or a freezer for freezing to obtain the methane combustible ice of the sand filling pipe. The volume ratio of the methane solution to the sand grains is that the volume ratio of the methane solution to the sand grains is 1: 5; the thickness of the cotton or the cloth is 5cm, the freezing temperature is set to be-10 ℃, and the freezing time is 2 d; the sand grains comprise the following components in percentage by mass: 95% quartz and 5% chlorite.
A method for applying the methane combustible ice of the sand-filled pipe specifically comprises the following steps:
(5) calculating the total volume of dissolved methane in the sand-filled pipe;
(11) measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; the formula B is that R ═ VMethane/VWater (W)；
(12) The total volume Q1 of the dissolved methane in the sand-packed pipe is calculated to be 12.6ml
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1 ═ VWet×R。
(2) Displacing the sand-filled pipe methane combustible ice by using an injection liquid according to a laboratory core holder displacement method under the displacement condition of-10 ℃, using a displacement agent of 6% propionic acid, collecting methane gas and measuring the volume of the methane gas to be Q2-11.5 ml;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: the displacement efficiency is Q2/Q1 multiplied by 100 percent to 91.3 percent.
Example 7
The embodiment 7 of the invention discloses a method for generating methane combustible ice of a sand-filled pipe in a laboratory and a displacement gas production method.
A method for generating methane combustible ice of a sand-packed pipe specifically comprises the following steps:
(1) weighing the following raw materials in percentage by mass: mixing 10% of diethylene glycol ethyl ether and 90% of water uniformly to obtain a methane dissolving agent;
(2) dissolving methane in a methane dissolving agent to obtain a saturated methane solution; the temperature and pressure during the dissolution process are 20 deg.C and 1.0 × 105Pa; the solubility of methane in 10% diethylene glycol ethyl ether was 28.6%;
(3) and uniformly mixing the methane solution and the sand grains to thoroughly soak the sand grains, adding the mixture into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe or the cloth in a refrigerator or a freezer for freezing to obtain the methane combustible ice of the sand filling pipe. The volume ratio of the methane solution to the sand grains is that the volume ratio of the methane solution to the sand grains is 1: 5; the thickness of the cotton or the cloth is 5cm, the freezing temperature is set to be-10 ℃, and the freezing time is 2 d; the sand grains comprise the following components in percentage by mass: 70% quartz and 30% feldspar.
A method for applying the methane combustible ice of the sand-filled pipe specifically comprises the following steps:
(6) calculating the total volume of dissolved methane in the sand-filled pipe;
(11) measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; the formula B is that R ═ VMethane/VWater (W)；
(12) The total volume Q1 of the dissolved methane in the sand-packed pipe is calculated to be 19.7ml
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1 ═ VWet×R。
(2) Displacing the sand-filled pipe methane combustible ice by using injection liquid according to a displacement method of a laboratory core holder, wherein the displacement condition is-10 ℃, 4% of HF is used as a displacing agent, and methane gas is collected and measured, and the volume of the methane gas is Q2-17.8 ml;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: the displacement efficiency is Q2/Q1 multiplied by 100 percent to 90.4 percent.
Example 8
The embodiment 8 of the invention discloses a method for generating methane combustible ice of a sand-filled pipe in a laboratory and a displacement gas production method.
A method for generating methane combustible ice of a sand-packed pipe specifically comprises the following steps:
(1) weighing the following raw materials in percentage by mass: uniformly mixing 5% of diethylene glycol monobutyl ether, 5% of isoamyl acetate and 90% of water to obtain a methane dissolving agent;
(2) dissolving methane in a methane dissolving agent to obtain a saturated methane solution; the temperature and pressure during the dissolution process are 20 deg.C and 1.0 × 105Pa; the solubility of methane in 5% diethylene glycol butyl ether, 5% isoamyl acetate and 90% water is 34.5%;
(3) and uniformly mixing the methane solution and the sand grains to thoroughly soak the sand grains, adding the mixture into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe or the cloth in a refrigerator or a freezer for freezing to obtain the methane combustible ice of the sand filling pipe. The volume ratio of the methane solution to the sand grains is that the volume ratio of the methane solution to the sand grains is 1: 5; the thickness of the cotton or the cloth is 5cm, the freezing temperature is set to be-10 ℃, and the freezing time is 2 d; the sand grains comprise the following components in percentage by mass: 95% quartz and 5% calcite.
A method for applying the methane combustible ice of the sand-filled pipe specifically comprises the following steps:
(7) calculating the total volume of dissolved methane in the sand-filled pipe;
(11) measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; the formula B is that R ═ VMethane/VWater (W)；
(12) The total volume Q1 of the dissolved methane in the sand-packed pipe is calculated to be 23.8ml
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1 ═ VWet×R。
(2) Displacing the methane combustible ice of the sand-filled pipe by using injection liquid according to a displacement method of a laboratory core holder, wherein the displacement condition is-10 ℃, a displacing agent is 6% HCl + 2% HF, methane gas is collected, and the volume of the methane gas is measured to be Q2-22.4 ml;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: the displacement efficiency is Q2/Q1 multiplied by 100 percent, 94.1 percent.
The invention provides a simple and feasible method for generating methane combustible ice of a sand filling pipe in a laboratory and a displacement gas production method, which can be used for manufacturing the sand filling pipe according to mineral components or real rock powder of a combustible ice rock stratum, simulating and generating the combustible ice sand filling pipe at real stratum pressure, real stratum temperature and real stratum rock, particularly providing a simple and rapid method and an experimental device for selecting an optimal combustible ice rapid supercooling nano liquefying agent, an optimal injection mode and an optimal injection speed, and providing technical and theoretical bases for selecting the optimal method for exploiting the combustible ice methane gas.
The method for generating methane combustible ice for the sand-filled pipe in the laboratory and the displacement gas production method provided by the invention can be simply and conveniently applied in a large amount in the laboratory, have wide practicability, have great influence on national energy strategy, energy demand and energy economy, and are difficult to estimate economic benefit and social benefit.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A method for generating methane combustible ice of a sand-packed pipe is characterized by comprising the following steps:
(1) weighing the raw materials according to the methane dissolving agent, and uniformly mixing to obtain the methane dissolving agent; the methane dissolving agent MST comprises the following components in percentage by weight: 0% -40% of diethylene glycol butyl ether, 0% -10% of tert-butyl alcohol, 0% -20% of polypropylene glycol, 0% -15% of polyvinyl alcohol, 0% -10% of sodium dodecyl sulfate, 0% -23% of ethylene glycol ethyl ether acetate, 0% -11% of ethyl acetoacetate, 0% -40% of diethylene glycol butyl ether, 0% -40% of isoamyl butyrate, 0% -40% of isoamyl acetate, 0% -40% of isooctyl acrylate and 0% -40% of butyl butyrate, and the balance of water is 100%;
(2) dissolving methane in a methane dissolving agent to obtain a saturated methane solution; the dissolving process is carried out at normal temperature and normal pressure; the volume ratio of the methane to the methane dissolving agent is (0.1-20.0): 1.0;
(3) uniformly mixing a methane solution and sand grains to thoroughly soak the sand grains, adding the sand grains into a sand filling pipe to be compacted, wrapping cotton or cloth which is soaked by water outside the sand filling pipe, and placing the sand filling pipe in a refrigerator or a freezer for freezing to obtain the methane combustible ice of the sand filling pipe, wherein the volume ratio of the methane solution to the sand grains is (1-2): (3-6); the thickness of the cotton or cloth is 3-5 cm, the freezing temperature is-10-18 deg.C, and the freezing time is 2-3 d;
the sand grains comprise sand grains obtained by grinding combustible ice stratum rocks or sand grains prepared according to stratum mineral components.
2. A sand-filled pipe methane combustible ice, which is prepared by the method of claim 1.
3. Use of the sand-packed methane combustible ice of claim 2 in laboratory research of combustible ice.
4. The application of the sand-packed pipe methane combustible ice in laboratory research combustible ice according to claim 3 is characterized by comprising the following steps:
(1) calculating the total volume Q1 of dissolved methane in the sand-packed pipe;
(2) displacing the methane combustible ice of the sand-filled pipe by using the injection liquid according to the rock sample seepage characteristics measured in a laboratory or a displacement experiment method carried out in the laboratory, collecting methane gas and measuring the volume of the methane gas to be Q2;
(3) calculating the displacement efficiency according to the formula A by using Q1 and Q2; the formula A is as follows: displacement efficiency = Q2/Q1 × 100%.
5. The use of the sand-packed pipe methane combustible ice in laboratory research combustible ice according to claim 4, wherein the step (1) specifically comprises:
(11) measurement of methane solubility
Dissolving methane gas into V in volume by adopting drainage methodWater (W)Until saturated, the total volume of dissolved methane gas was recorded as VMethane(ii) a From VWater (W)And VMethaneCalculating according to a formula B to obtain the solubility R; the formula B is R = VMethane/VWater (W)；
(12) Calculating the total volume Q1 of dissolved methane in the sand-packed pipe
Metering the volume Q of methane solution added to a sand-packed pipeWetAnd calculating the total amount Q1 of dissolved methane gas in the sand-packed pipe according to a formula C: q1= QWet×R。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910741440.5A CN110501194B (en) | 2019-08-12 | 2019-08-12 | Preparation method and application of methane combustible ice of sand filling pipe in laboratory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910741440.5A CN110501194B (en) | 2019-08-12 | 2019-08-12 | Preparation method and application of methane combustible ice of sand filling pipe in laboratory |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110501194A CN110501194A (en) | 2019-11-26 |
| CN110501194B true CN110501194B (en) | 2022-03-08 |
Family
ID=68586341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910741440.5A Active CN110501194B (en) | 2019-08-12 | 2019-08-12 | Preparation method and application of methane combustible ice of sand filling pipe in laboratory |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110501194B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5052386B2 (en) * | 2008-03-31 | 2012-10-17 | 三井造船株式会社 | Gas hydrate manufacturing equipment |
| CN101710088A (en) * | 2009-12-17 | 2010-05-19 | 中国海洋石油总公司 | Method and device for testing formation and decomposition of gas hydrate |
| CN107676069A (en) * | 2017-10-23 | 2018-02-09 | 大庆东油睿佳石油科技有限公司 | A kind of device for simulating the exploitation of gas hydrates parallel water horizontal well chemical flooding |
| CN107701182A (en) * | 2017-10-23 | 2018-02-16 | 大庆东油睿佳石油科技有限公司 | A kind of device for simulating row's formula horizontal well chemical flooding exploitation of gas hydrate |
| CN108301816A (en) * | 2018-01-09 | 2018-07-20 | 中国石油大学(华东) | The method and apparatus that chemical agent influences gas hydrate dissociation characteristic evaluation |
-
2019
- 2019-08-12 CN CN201910741440.5A patent/CN110501194B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110501194A (en) | 2019-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103216219B (en) | A kind of CO 2/ N 2the method of underground replacement exploitation of gas hydrate | |
| Li et al. | Methane hydrate dissociation using inverted five-spot water flooding method in cubic hydrate simulator | |
| CN104031625B (en) | De-plugging agent and using method for hypotonic permeable Heterogeneous Sandstone Reservoirs | |
| CN102911654B (en) | Foaming agent for efficiently carrying fluid and sand for gas well and preparation method and application of foaming agent | |
| CN103224772B (en) | A kind of cementing slurry, Preparation Method And The Use | |
| CN105018103B (en) | A kind of soil-solidified-agent and preparation method thereof and application method | |
| CN103573231B (en) | The method for improving recovery ratio of sensitive heavy oil reservoir | |
| CN103333673B (en) | Deep low-damage acidizing fluid | |
| CN107965306A (en) | A kind of acid filling fracturing process | |
| BR112016011191B1 (en) | METHOD TO CONSOLIDATE SOLID MATERIALS DURING UNDERGROUND TREATMENT OPERATIONS | |
| CN103333667B (en) | Low pressure coefficient Gas Reservoir protection drilling fluid composition and preparation method | |
| CN103333666A (en) | Solid-free well-completion confining liquid and preparation method thereof | |
| CN108623248A (en) | A kind of charcoal is modified eco-concrete and preparation method thereof | |
| CN105295886B (en) | A kind of composite retarded acid | |
| CN108587588A (en) | A kind of water injection well injection agent and its preparation method and application | |
| CN104234680A (en) | Rapid thermal activation exploitation method for natural gas hydrate | |
| CN110501194B (en) | Preparation method and application of methane combustible ice of sand filling pipe in laboratory | |
| CN104046342B (en) | A kind of high temperature resistance Solid Free micro-foam drilling fluid or completion fluid | |
| CN113343417A (en) | Reconstruction and restoration method for water-resisting layer and surface soil layer based on mining surface crack | |
| CN106967402A (en) | A kind of acidification blocking remover and its construction method suitable for deep volcanic rock gas reservoir | |
| CN105298480A (en) | Fracture-cavity carbonate rock model, method for manufacturing same and application of fracture-cavity carbonate rock model | |
| CN102604604B (en) | Drilling fluid material and preparation and application thereof | |
| Lu et al. | Evaluation of carbon dioxide storage in the deep saline layer of the Ordovician Majiagou Formation in the Ordos Basin | |
| CN102120930A (en) | Oil reservoir modification acid liquor and oil production method by using same | |
| Li et al. | A review of research progress of vegetation concrete on coastal highway slope |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |